Fungi and bacteria resistant papermakers&#39; felts and process for preparing same



Patented Apr. 29, 1952 FUNGI AND BACTERIA RESISTANT PAPER- MAKERS FELTSAND PROCESS FOR PRE- PARING SAME Paul George Benignus, Belleville,Ill-., assignor to Monsanto Chemical Company, St. Louis, Mo., acorporation of Delaware No Drawing. Application November 12, 1946,Serial No. 709,105

Claims. (01. rim-138.5)

This invention relates to a process for the treatment of fibrousmaterials and more specifically to an improved process and compositionwhereby fibrous materials such as cotton, linen and other cellulosictextiles and fibers, and laid cellulosic materials, and fibrousproteinaceous materials such as woolen textiles and felts, particularlypapermakers felts, may be made highly and pergianently resistant toattack by fungi and baceria.

Papermakers felts are subject to rapid deterioration due to the activityof fungi and bacteria encountered in the paper mills white water system,in fact, severe mildew conditions have been experienced whereby theaverage life of untreated felts has been but one to two weeks, andtherefore, a number of preservative treatments have been developed forthe purpose of rendering the felts resistant to the deleterious activityof fungi and bacteria. However, in use, these felts are subjected togreat volumes of running water and, therefore, the preservatives arecontinuously and rapidly leached from the felts. There has not beendeveloped, prior to this invention, any preserving treatment forpapermakers' felts which will render the felt satisfactorily resistantto the severe leaching action of the paper mills white water.

When: fibrous materials are immersed in a bath containing a fungicidalor a bactericidal agent such as a solution of 8-hydroxyquinoline or achlorophenol, the treated fibrous material will possess fungicidal andbactericidal properties. However, subsequent wetting, soaking orlaundering of the fibrous materials so treated tends to remove thefungicidal or bactericidal agent and thereby substantially reduce theresistance of the fibrous material to the activity of fungi andbacteria. In order to fix the fungicidal agent onto the fabric, it hasbeen proposed to form a difiicultly soluble metallic salt of thefungicidal agent within the interstices of the fabric material. Sincethe metallic salts of many of the fungicidal agents as8-hydroxyquinoline and the chlorophenols are relatively insoluble inmost media for treating fibrous materials, it has been proposed toemploy a method whereby after immersion in a water soluble fungicidalagent,

som the metallic salts of which are relatively insoluble, the fabric isdrained and subsequently passed through a solution of a' water solublemetal salt as calcium, magnesium, or other alkaline earth acetatespzinc,-aluminum, -copper, cadmium or other heavy metal acetates 'or nitrateswhereby the metal salt of the fungicidal agent is precipitated on orwithin the fibrous material. This method of fixing the fungicidal agenton the fabric has certain disadvantages. For example, a fabric treatedby the two-bath method as has been hereinbefore described andsubsequently dried contains soluble salts which leach out when thefibrous material is subsequently laundered or subjected to weatheringconditions, and the relatively insoluble salts are not satisfactorilybonded to the fiber, thus the residual protection against fungi andbacteria is materially reduced. On the other hand, many of the bestknown fungicidal agents such as the heavy metal salts of substances suchas oxyquinoline (8-hydroxyquinoline) are too insoluble in water and inother liquid media to be suitable for the impregnation of fibrousmaterials for the reason that an adequate concentration of the agentcannot be provided in the bath for the proper treatment of the fabric.Also, the use of these heavy metal salts has been impeded for the reasonthat there has been no satisfactory method for uniformly dispersing andbonding an insoluble fungicide throughout the fibrous material.

One of the objects of the present invention is to provide a novelprocess whereby fibrous materials such as textiles and more particularlypapermakers' felt may be impregnated with sufficient amounts ofuniformly dispersed relatively insoluble metallic salts of8-hydroxyquinoline and derivatives of 8-hydroxyquinoline to render thefibrous material permanently and effectively resistant to the action offungi and bacteria.

A further object is to provide a papermakers felt treated with afungicidal composition which felt is highly and permanently resistant tothe severe leaching action of continuously running water, particularly,paper mill white water.

Other objects will become apparent from thefollowing description andexamples:

The improved fungi-proofing process of this invention comprises thepreparation of a treating solution by first preparing a waterdispersible paste concentrate of a copper, zinc or cadmium salt of an8-hydroxyquinoline, with a film forming protective colloid such asmethyl cellulose in the presence of a wetting agent such as dodecylbenzene sodium sulfonate and dispersing a proper amount of the pasteconcentrate in a water solution of a Water soluble amine-aldehyderesinforming composition such as an alkyl ether of an alkylol melaminecontaining an acidic condensation catalyst. Papermakers felt is thenimpregnated with the treating solution, for example, by immersing thefelt in the solution at room temperature. The felt is subsequently driedand cured for a short time at an elevated temperature. The result ofthis process up to this point is a uniform deposition of the fungicidalagent on and possibly within the fiber and firmly bonded to the fiber orsealed within thefiber by the film of protective colloid and made waterresistant by the melamine or urea-formaldehyde type resin. However, dueto the severe leaching action of the large volumes of water encounteredin using papermakers felts, and the abrasive action of the pulp on thefelt, I have found that it is necessary to further protect theimpregnated felt or fibrous material by giving the felt a further waterrepelling treatment comprising treating the impregnated felt with anaqueous dispersion comprising a water repelling agent such as anN-methylol alkylamide or an N,N diacyl diamino methane wherein the alkylor acyl substituent is a long carbon chain of from C12 to C28, adispersing agent such as ammonium oleate, triethanol amine oleate,Z-amino-Z-methyl-l-propanol oleate or stearate and a water solubleresinforming composition such as an alkyl ether of mono, di or tetramethylol melamine, for example, the dibutyl ether of tetra methylolmelamine or an amine-aldehyde resin-forming composition such asurea-formaldehyde and an acidic catalyst to effect the propercondensation of the resin-forming composition. The treated felt orfibrous material is then dried at 215 F. and heat cured at a temperatureof from 250 to 320 for 3 to 20 minutes. A papermakers felt treated inthis manner is made highly and permanently resistant to the activity offungi and bacteria even under the most severe leaching conditions.

The fungicidal agents I have found most desirable for'the purpose ofthis invention are the copper, zinc or cadmium salts of8-hydroxyquinoline, 5,7-dichlcr-8-hydroxyquinoline, or 5,7-di-'brom-S-hydroxyquinoline, although other metallic salts may be employedsuch as the aluminum or calcium salts. However, the copper salts aremuch to be preferred since they are far more effective from thestandpoint of insolubility and permanency when incorporated in thefibrous material. I have found it highly desirable to use these metallicquinolinolates in a very finely divided form of ultimate particle sizeof from 1 to 10 microns.

While there are many wetting agents which are suitable for the purposeof this invention, I have found the following to be particularlysatisfactory: dodecyl benzene sodium sulfonate, decyl benzene succinate,sodium lauryl sulfate, cocoanut oil monoglyceride monosulphate, mixedpetroleum sulfonates, and the polyglycol ethers of diisobutylene phenol.

The protective colloid may be selected from methyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, al inates, gelatin, casein, soyaproteins, starches, lecithin and water soluble gums. There are, however,many other suitable protective colloids. In general, the methylcellulose and the carboxy methyl cellulose are most desirable as theprotective colloid, not only because they have the desired film-formingproperties but they are less susceptible than the proteina-ciousmaterials to attack by micro-organisms.

The permanent bonding of the fungicidal agent to the fiber and a highdegree of water resistance is imparted to the fibrous materials byreason of the resin which may be selected from various urea-formaldehydeand melamine resins. The same resin-forming composition may be used inboth the impregnation step and in the second protective step whereinadditional water repellency is imparted to the impregnated felt. Theseresins must be used in the treating solutions in the form of watersoluble 01' water dispersible resin-forming compositions. For thepurpose of this invention, I prefer to use a resin-forming compositionOf the type illustrated by the alkyl ethers of an alkylol melamine suchas the methyl ether of methylol melamine, the methyl ether of dimethylolmelamine or the di'butyl ether of tetramethylol melamine. However, otheramine aldehyde resin-forming compositions may be used in either stepsuch as those containing urea-formaldehyde, melamine-formaldehyde,dimethylol urea, or dimethylol urea ethers of lower saturated aliphaticalcohols of one to six carbon atoms. An acidic catalyst is used inconjunction with the resinfcrming composition to effect the propercondensation and formation of the resin. While I prefer to usecyclohexyl ammonium phosphate as the catalyst, di-ammonium phosphate,phosphoric acid, acetic acid or formic acid may be substituted. However,in the second treating step, wherein the solution is maintained at a pHof 9 to 10 by the use of a fugitive base, the catalyst should beselected from cyclohexyl ammonium phosphate and di-ammonium phosphate.On the other hand, the copending application No. 551,077 and now PatentNo. 2,537,677 discloses that the usual acidic condensation catalyst maybe omitted where a N,N'-diacyl diamino methane is used in the secondstep of the process. Inthe presence of a N ,N diacyl diamino methane,the amine-aldehyde condensation will proceed in a neutral solution. But,in this process a catalyst such as the above described ammonium saltsmay be used if desired. The amount of catalyst is generally about 3 to4% of the weight of the melamine or urea-formaldehyde resin used.

The impregnation with the fungicidal or bac tericidal agent may beaccomplished in any desired manner, for example, by immersion of thefelt in a vessel containin the treating solution which may be at roomtemperature and, the impregnation may be handled either as a continuousoperation or as a batch process. For the treatment of papermakers felt Ihave obtained excellent results by using a padder, mangle or rolls withan adjusted nip so as to give the desired pick-up of the fungicidalcomposition. In most instances, a pick-up of the fungicidal agentequivalent to to 2% of the weight of the untreated felt is mostdesirable. Likewise, the drying operation may be accomplished in anydesired manner, for example, by exposing the respectively treatedsurfaces simultaneously or successively to air streams which may be atroom temperature or at some elevated temperature below the charringpoint of the fibrous material, preferably about 215 F. With regard tocuring,

variations with reference to the time and tem-' perature of the curedepend entirely upon the heat setting properties of the resin selected.For

example: When I use a melamine type resinforming composition, thefollowing table indicates the temperature curing time and for the resinafter all of the water has been removed from the felt:

Time (minutes) Temperature Likewise, the water soluble urea-formaldehyderesin-forming composition may be cured in 3 to 20 minutes atatemperatureof 250 to 300 F.

In the second step of this process, high permanent water repellency isimparted to the impregnated felt. The N,N' diacyl diamino methane may beprepared in the manner described in U. S. Patent No. 2,365,813. Sinceboth the N,N diacyl diamino methane and the resins which have beenhereinbefore described, are water insoluble the application to thetextile fiber is most conveniently made by means of an aqueoussuspension or dispersion of the diamide, the resinforming compositionand a dispersing agent comprising the fatty acid salt of a fugitivebase. The fatty acid used to form the dispersing agent may be any fattyacid saturated, unsaturated or hydroxylated and should have a carbonchain length of at least 12 to 28 carbon atoms. Accordingly, there maybe employed lauric, stearic, palmitic or oleic acids or other fattyacids contained within the above length of carbon chain lengths. Thefatty acid salt is preferably the ammonium salt although other basescapable of volatilizing at the temperature at which the heat treatmentis carried out may also be used. Examples of such bases are morpholine,pyridine, cyclohexlamine and 2-amino-2-methyll-propanol. The dispersioncontains in addition sufficient ammonia or other fugitive base to bringthe hydrogen ion concentration of the dispersion over to the alkalineside of neutrality and preferablyrto the point where the pH thereof willbe within the range of from 9.0 to 10.0. Within this pH range thedispersed diacyl diamino methane and aminealdehyde resin-formingcompositions when reduced by suitable means to a particle of from 0.5 to10.0 microns is a stable emulsion both at room temperature and attemperatures as high as 80 C.

Application of the dispersion to the fabric may be made directly byimmersion as by treatment in a jig or padder or alternatively byspraying the dispersion upon the textile fabric. While the treatment ofthe fiber is most conveniently carried out by means of a singledispersion containing both the diacyl diamino methane, the resinformingcomposition and the dispersing agent the application may be made bysuccessive treatments of the fabric with a separate dispersion of thediamide and dispersing agent and later with the resin-formingcomposition.

The amount of pick-up of materials from the second immersion dependsupon the particular use to which the felt is to be put. However, solidsfrom this immersion may be incorporated into the felt equivalent to to125% of the weight of the untreated felt.

The application of the aqueous dispersion to the textile product maytake place at any temperature between room temperature and up totemperatures as high as 175 F. The treated felt is again .dried eitherat room temperature or in heating air, briefly at about 215 F. After themoisture has been evaporated from the felt the temperature is raised tobetween 250 F. and 320 F. for 2 to '20 minutes.

EXAMPLE I A water dispersible paste concentrate is first preparedcontaining:

2.00 parts of copper 8-quinolinolate 20.00 parts of 5% aqueous solutionof methyl eellulose 0.05 part of decyl benzene sodium sulfonate positionof an ether of dimethylol melamine containing 0.60 part of a 10% aqueoussolution of cyclohexyl ammonium phosphate.

The papermakers felt is then treated with the prepared fungi proofingcomposition at room temperature using a mangle. After drying, at 215 F.,the treated felt is cured for 3 minutes at a temperature of 300 F.

A second dispersion is prepared containing:

Per cent NN' distearoyl diamino methane 5.0 Solution of a resin-formingcomposition of dibutyl ether of tetra methylol melamine (solids) 10.5Stearic acid 3.5 Ammonium hydroxide 28% 4.0 Cyclohexyl ammoniumphosphate 0.4

Water Balance The dispersion is prepared by adding the melted fatty acidto the water, adding the ammonia until a pH of 9.0 to 10 is reached.Finely divided N,N distearoyl diamino methane (particle size below 10microns) is added and the mixture passed through a colloid mill. Theresin-forming melamine composition added and the whole mixture againpassed through the colloid mill. The felt is immersed in the dispersion,at a, temperature between room temperature and F., the amount of pick-upbeing controlled by the nip of the padder rolls. The melt is then driedat 215 F. and finally heat cured at 300 F. for 5 minutes.

The felt, treated as described above, was leached for 1,000 hours withrunning tap water, and the permanence of the fungi and bacteria proofingtreatment is illustrated by the following table:

Per cent of Copper S-Quinolinolate in the Felt on a Weight Basis HoursLeeched With Running Tap Water Samples of the felt which were leached1,000 hours in running tap water were inoculated with each of thefollowing organisms:

Chaetomium globosum, Metarrhz'ez'um sp., Aspergz'llus mger andPenicillium sp. and then incubated for customary periods of time.

Results of the biological test are given below in Table II.

Table II.Fu'ngus resistance of copper 8-quinolinolate treated feltleached 1,000 hours in running water Organism Fungus gacggi'gy on theChaetomium globosum No growth of the organism on the sample.

Do: Do.

Metarrhjzium s17 Aspergdlus nz'ger Penicillium sp The zinc or cadiumsalts of 8-hydroxyquinoline were substituted in the above example withsubstantially the same results.

The proportion of the ingredients may be varied depending upon theamount of preservative and resin desired in the finished felt. However,the normal desirable range which may be used in varying the proportionsof the various ingredients in the impregnation treatment are as follows:

LOO-3.0% copper, zinc or cadium s-quinolinolate,5.7-dichlor-8-quinolino1ate or 5,7-dibrom- 8-quinolinolate 10.00-30.0%aqueous solution methyl cellulose 0.05-2.0% wetting agent 0.50-20.0%melamine or urea-formaldehyde resin in a resin-forming composition form0.15-3.0% 10% aqueous solution of catalyst 88.30--52.0% water Inaddition, the normal desirable range which may be used in varying thepreparations of the various ingredients in the step wherein the waterrepellency is insured, is as follows:

Per cent N,N' diacyl diamino methane 3.5- Melamine or amine-formaldehyderesin (solids) 8.0-24 Fatty acids 3.5- 8 Fugitive base 4.0- 8.0Condensation catalyst 0.0- 1.0 Water Balance The dispersion may also bevaried somewhat by replacing up to 50% of the N,Nf diacyl diaminomethane with other well known water repellents as aluminum stearate, aparafiin wax, or N- methylol alkyl amide wherein the alkyl chain has 12to 28 carbon atoms.

EXAMPLE II Water dispersz'ble paste concentrate 3.00 parts of copper5,7-dichlor-8-quinolinolate 0.75 parts of decyl benzene sodium succinate30.00 parts of carboxy methyl cellulose Ready to use treating solution33.75 parts of the above paste concentrate 4.00 parts of a water solubleurea-formaldehyde resin-forming composition 0.16 part of phosphoric acid62.19 parts of water The felt is run through the treating solution atroom temperature, oven dried at 215 F. and finally cured by heating for10 minutes at 275 F.

I'he treating solution for imparting increased water repellency to thefelt may be prepared as follows:

Per cent N,N distearoyl diamino methane 3.5 N methylol stearamide 3.5

Urea-formaldehyde resin-forming composition (solids) 15.0 Oleic acid 3.5Triethanol amine 4.0 Cyclohexyl ammonium phosphate 0.6

Water Balance The dispersion is made as described in Example I. The feltis run through the treating solution at 100 F., dried at 215 F. andagain cured by heating for 10 minutes at 275 F.

The 1,000-hour leaching test gave substantially the same results as inExample I, and innoculation of the leached samples with Chaetomium 8globosum, M etarrhizium sp., Aspergillus niger and Penicillium sp. andincubation produced no growth of any organism on the samples.

The zinc and cadmium salts of 5,7-dichlor-8- quinolinolate indicatedsubstantially the same results, that is, high and permanent resistanceto fungal and bacterial activity.

EXAMPLE III Water dispersz'ble paste concentrate 1.00 part of copper5,7-dibrom-8-quinolinolate 0.05 part of a poly-glycol ether ofdi-isobutylene phenol 10.00 parts of casein Ready to use treatingsolution 11.05 parts of above paste concentrate 5.00 parts of a watersoluble ether of inethylol melamine 0.15 part of diammonium phosphate83.80 parts of water The felt is run through the treating solution atroom temperature, oven dried at 215 F. and finally cured by heating for3 minutes at 300 F.

A satisfactory emulsion for the second step of the process comprises thefollowing:

Per cent N,N' distearoyl diamino methane 2.0 Aluminum stearate 2.0

Water soluble resin-forming composition of the methyl ether ofdimethylol melamine" 8.0

Laurie acid 5.0 2-amino-2-methyl-l-propanol 5.0 Diammonium phosphate 0.3Water Balance The dispersion is prepared in the manner de scribed inExample I, and the felt run through the dispersion until a weight ofsolids equivalent to about 40% of the weight of the dry untreated feltis picked up. The felt is dried at 215 F. and finally heat cured for 5minutes at 280 F.

The 1,000-hour leaching test gave substantially the same results as inExample I, and innoculation of the leached samples with Chaetomiumglobosum, Mctarrhizium sp., Aspergillus niger and Peniciiiium sp., andincubation produced no growth of any organism on the samples.

The zinc and cadmium salts of 5,7-dibrom-8- quinolinolate indicatedsubstantially the same results, that is, high and permanent resistanceto fungal and bacterial activity.

I claim:

1. A process for increasing the resistance of fibrous materials to theactivity of fungi and bacteria comprising contacting the fibrousmaterial With an aqueous composition containing 'a relatively waterinsoluble 8-quinolinolate selected from the group consisting of copper,zinc and cadmium derivatives of S-quinolinol, 5,7-dibrom- S-quinolinoland 5,7-dichlor-8-quinolinol, a filmforming protective colloid, asurface active agent, a resin-forming amine-aldehyde composition, and anamine-aldehyde condensation catalyst; drying the impregnated fibrousmaterial; heating the impregnated fibrous material for 3 to 20 minutesat 250 to 320 F.; contacting the impregnated fibrous material with anaqueous composition containing a water repellent, a resin-formingaminealdehyde composition, an amine-aldehyde condensation catalyst and adispersing agent comprising a fatty acid salt of a fugitive base; dryingthe impregnated fibrous material, and heating the impregnated fibrousmaterial for 3 to 20 minutes at 250-320 F.

2. A process for increasing the resistance of 'fibrousimaterials to theactivity of fungi and baciteria comprising contacting the fibrousmaterial with an aqueous composition containing 1-3% of a relativelyWater. insoluble B-quinolinolate. selected from thegroup consisting ofthe copper, zinc and cadmium derivatives of S-quinolinol, 5,7dibrom-il-quinolinol and 5,7-dichlor-8-quinolinol,

05-294; "of a. film-forming protective -colloid,

condensation catalyst, 3.5-8% of a dispersing agent; drying theimpregnated fibrous material and heat curing the impregnated fibrousmaterial fror's zo minutes at 250-320 1 3. A process for increasing theresistance of fibrous materials to the activity of fungi and bacteriacomprising contacting the fibrous material with an aqueous compositioncontaining 1-3% of a relatively water insoluble B-quinolinolate selectedfrom the group consistin of the copper, zinc and cadmium derivatives ofS-quinolinol, 5,7- dibrom-B-quinolinol and 5,7-dichlor-8-quinolinol,0.5-2% of film-forming protective colloid, 05-20% of a resin-formingmelamine ether, and ill-3.0% of a melamine condensation catalyst; dryingthe impregnated fibrous material; heat curing the impregnated fibrousmaterial for 3 to minutes at 250-320 F.; contacting the heat curedimpregnated fibrous material with an aqueous composition containing3-15% of a diacyl diamino methane wherein the acyl group is derived froma fatty acid having 12 to 28 carbon atoms, 0.5-20 of a resin-formingmelamine ether, 01-30% of a melamine condensation catalyst, 3.5-8% of afatty acid, and 4-8% of a fugitive base; drying the impregnated fibrousmaterial and heat curing the impregnated fibrous material for 3-20minutes at 250-320 F.

4. Process of claim 3 wherein the resin-forming melamine ether is thetetra butyl ether of tetra methylol melamine.

5. A process for increasing the resistance of fibrous materials to theactivity of fungi and bacteria comprising contacting the fibrousmaterial with an aqueous composition containing l-3% of a relativelywater insoluble 8-quino1inolate selected from the group consisting ofcopper, zinc and cadmium derivatives of 8-quinolinol,5,7-dibrom-El-quinolinol and 5,7-dichlor-8-quinolinol, 0.5-2% of afilm-forming protective colloid, 05-20% of the resin-forming dibutylether of tetra methylol melamine, and 01-30% of a melamine ethercondensation catalyst; drying the impregnated fibrous material; heatcuring the impregnated fibrous material for 3 to 20 minutes at 250-320F.; contacting the heat cured impregnated fibrous material with anaqueous composition containing 3-15 of N,N' distearoyl diamino methane,05-20% of the resin-forming dibut-yl ether of tetra methylol melamine,(Ll-3.0% of a melamine ether condensation catalyst, 3.5-8

of a fatty acid, and 4--8% of a fugitive base; drying the impregnatedfibrous material and heat 10 curing the impregnated fibrous material for3-20 minutes at 250-320 F.

6. A process for increasing the resistance of papermakers felts to theactivity of fungi and bacteria comprising contacting the felt with anaqueous composition containing 1-3% of a relatively water insolubleS-quinolinolate selected from the group consisting of copper, zinc andcadmium derivatives of B-quinolinol, 5,7-dibrom- 8-quino1inol and5,7-dichlor-8-quinolinol, 0.5-2% of a film-forming protective colloid,0.05-2% of a surface active agent, 05-20% of a resin-forming melamineether, and (Ll-3.0% of a melamine ether condensation catalyst; dryingthe impregnated felt; heat curing the impregnated felt for 3 to 20minutes at 250 to 320 F.; contacting the heat cured impregnated feltwith an aqueous composition containing 3 to 15% of a diacyl diaminomethane wherein the acyl group is derived from a fatty acid having 12 to28 carbon atoms, 5 to 25% of a resin-forming melamine ether, 3 to 8% ofa fatty acid salt of a fugitive base; drying the impregnated felt, andheat curing the impregnated felt for 3 to 20 minutes at 250 to 320 F.

7. A process for increasing the resistance of papermakers felts to theactivity of fungi and bacteria comprising dispersing a paste concentratecomprising two parts of copper-S-quinolinolate, 20 parts of 5% aqueoussolution of methyl cellulose and 0.05 part of a Wetting agent with anaqueous resin-forming composition containing parts of water, 2 parts ofthe dibutyl ether of tetra methylol melamine and 0.6 part of 10% aqueoussolution of cyclohexyl ammonium phosphate; contacting the felt with theabove described water dispersion; drying the impregnated felt; heatcuring the impregnated felt for 3 to 20 minutes at 250-320 F.;contacting the cured impregnated felt with an aqueous dispersioncontaining 5% N,N' distearoyl diamino methane, 10% of a resin-formingdibutyl ether of tetra methylol melamine; 3.5% of stearic acid, 4% of28% ammonium hydroxide and 72.5% Water; drying the treated felt and heatcuring for 3 to 20 minutes at 250-320 F.

8. A water repellent papermakers felt possessing increased resistance tothe activity of fungi and bacteria comprising a papermakers feltcontaining within its interstices a relatively water insoluble8-quinolinolate selected from the group consisting of the copper,cadmium and zinc derivatives of 8-quinolinol, 5,7-dibrom-8-quinolinoland 5,V-dichlor-8-quin0linol, a water repellent, and a resinousamine-aldehyde condensation product; said felt having been impregnatedwith an aqueous dispersion containing the S-quinolinolate, a protectivecolloid, a wetting agent, a resinforming amine-aldehyde composition andan amine-aldehyde condensation catalyst, dried and heated to eifect thecondensation of the aminealdehyde composition to form the resinousaminealdehyde condensation product, and having been subsequently treatedwith an aqueous dispersion containing the water repellent, a dispersingagent, and the resin-forming amine-aldehyde composition; dried andheated to effect the condensation of the amine-aldehyde composition toform the resinous condensation product.

9. A water repellent papermakers felt possessing increased resistance tothe activity of fungi and bacteria comprising a paper-makers feltcontaining within its interstices a relatively water in soluble8-quinolinolate selected from the group consisting of the copper,cadmium and zinc dcrivatives of il-quinolinol, 5,7-clibrom-8-quinolinoland 5,7-dichlor-8-quinolinol, a N,N diacyl diamino methane wherein theacyl group is derived from fatty acids of 12 to 28 carbonatoms, and aresinous melamine ether condensation product; said felt having beenimpregnated with an aqueous dispersion containing the 8-quinolinolate, aprotective colloid, a wetting agent, a resin-forming melamine ether anda melamine ether condensation catalyst, dried and heated to effect thecondensation of the melamine ether to form the resinous melaminecondensation product, and having been subsequently treated with anaqueous dispersion containing the N,N diacyl diamino methane, adispersing agent, and the resin-forming melamine ether, dried and heatedto effect the condensation of the melamine ether to form the resinouscondensation product.

10. A water repellent papermakers felt possessing increased resistanceto the activity of fungi and bacteria comprising a papermakers feltcontaining within its interstices copper-8-quinolinolate, N,N distearoyldiamino methane and a resinous condensation product of the dibutyl etherof tetra methylol melamine; said felt having been impregnated with anaqueous dispersion containing the copper-8-quinolinolate, a protectivecolloid, a wetting agent, a resin-forming dibutyl ether of tetramethylol melamine, and a melamine ether condensation catalyst; dried andheat cured to effect the condensation of the melamine ether to form theresinous melamine condensation product, and subsequently treated with anaqueous dispersion containing the N,N' distearoyl diamino methane, adispersing agent comprising a fatty acid salt of a fugitive base, and aresin-forming dibutyl ether of tetra methylol melamine, dried and heatedto form the resinous melamine condensation product.

PAUL GEORGE BENIGNUS.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS

1. A PROCESS FOR INCREASING THE RESISTANCE OF FIBROUS MATERIALS TO THEACTIVITY OF FUNGI AND BACTAERIA COMPRISING CONTACTING THE FIBROUSMATERIAL WITH AN AQUEOUS COMPOSITION CONTAINING A RELATIVELY WATERINSOLUBLE 8-QUINOLINOLATE SELECTED FROM THE GROUP CONSISTING OF COPPER,ZINC AND CADMINUM DERIVATIVES OF 8-QUINOLINOL, 5,7,-DIBROM8-QUINOLINOLAND 5,7-DICHLOR-8-QUINOLINOL, A FILMFORMING PROTECTIVE COLLOID, ASURFACE ACTIVE AGENT, A RESIN-FORMING AMINE-ALDEHYDE COMPOSITION, AND ANAMINE-ALDEHYDE CONDENSATION CATALYST; DRYING THE IMPREGNATED FIBROUSMATERIAL; HEATING THE IMPREGNATED FIBROUS MATERIAL FOR 3 TO 20 MINUTESAT 250 TO 320* F.; CONTACTING THE IMPREGNATED FIBROUS MATERIAL WITH ANAQUEOUS COMPOSITION CONTAINING A WATER REPELLENT, A RESIN-FORMINGAMINEALDEHYDE COMPOSITION, AN AMINE-ALDEHYDE CONDENSATION CATALYST AND ADISPERSING AGENT COMPRISING A FATTY ACID SALT OF A FUGITIVE BASE; DRYINGTHE IMPRENATED FIBROUS MATERIAL, AND HEATING THE IMPREGNATED FIBROUSMATERIAL FOR 3 TO 20 MINUTES AT 250-320* F.